Composite articles including a fluoropolymer blend

ABSTRACT

A composite article is provided which includes a blend component comprising a vinylidene fluoride containing fluoropolymer and a substantially non-vinylidene fluoride containing fluoropolymer, and a component including a substantially non-fluorinated polymer having pendant amine groups intimately bonded to the blend component. Increased adhesion is observed by a greater peel strength value between the blend component and a substantially non-vinylidene fluoride containing fluoropolymer when compared to a peel strength value between a substantially non-vinylidene fluoride containing fluoropolymer and the substantially non-fluorinated polymer having pendant amine groups.

BACKGROUND OF THE INVENTION

Fluoropolymers, or fluorine-containing polymers, are a commerciallyimportant class of materials. Fluoropolymers include, for example,crosslinked fluorocarbon elastomers and semi-crystalline or glassyfluorocarbon plastics. Fluorocarbon plastics (or fluoroplastics) aregenerally of high thermal stability and are particularly useful at hightemperatures. They also exhibit extreme toughness and flexibility atvery low temperatures. Many of these fluoroplastics are almost totallyinsoluble in a wide variety of solvents and are generally chemicallyresistant. Some have extremely low dielectric loss and high dielectricstrength and many have unique nonadhesive and low-friction properties.See, for example, F. W. Billmeyer, Textbook of Polymer Science, 3rd ed.,pp. 398-403, John Wiley & Sons, New York (1984).

Fluorocarbon elastomers, particularly the copolymers of vinylidenefluoride with other ethylenically unsaturated halogenated monomers, sucha hexafluoropropene, have particular utility in high temperatureapplications, such as seals, gaskets, and linings. See, for example, R.A. Brullo, “Fluoroelastomer Rubber for Automotive Applications,”Automotive Elastomer & Design, June 1985, “Fluoroelastomer Seal UpAutomotive Further,” Materials Engineering, October, 1988, and W. M.Grootaert, et al., “Fluorocarbon Elastomers,” Kirk-Othmer, Encyclopediaof Chemical Technology, Vol. 8, pp. 990-1005 (4th ed., John Wiley &Sons, 1993).

Fluoroplastics, particularly polychlorotrifluoroethylene,polytetrafluoroethylene, copolymers of tetrafluoroethylene,hexafluoropropylene, perfluoropropyl vinyl ether and poly (vinylidenefluoride), have numerous electrical, mechanical, and chemicalapplications. Fluoroplastics are useful, for example, in wire coatings,electrical components, seals, solid and lined pipes, and piezoelectricdetectors. See, for example, “Organic Fluorine Compounds,” Kirk-Othmer,Encyclopedia of Chemical Technology, Vol. 11, pp., 20, 21, 32, 33, 40,41, 50, 52, 62, 70, 71 (John Wiley & Sons, 1980).

In the automotive industry, for example, increased concern withevaporative fuel standards has led to the need for fuel systemcomponents that have improved barrier properties. This helps reduce thepermeation of fuel vapors through automotive elements such as fuelfilter lines, fuel supply lines, fuel tanks, and other elements of anautomobile fuel system. Multi-layer tubing and other articles containinga fluorinated layer have been used in such automotive elements toprovide a chemically resistant permeation barrier. Multi-layer articlesare also useful in a number of other industries including, for example,the chemical processing and/or handling industries, and the electricaland electronics industries. Such multi-layer articles can include one ormore other layers that can add strength, rigidity, or other mechanicalproperties.

Multi-layer compositions comprising a fluorinated polymer layer and apolyamide or polyolefin layer are known. See, for example, U.S. Pat. No.4,933,090 (Krevor) which discloses laminate tubular articles that caninclude layers of fluorocarbon elastomers, and International PublicationNo. WO 93/1493 (LaCourt) which discloses a laminar film structure thatincludes a polyimide and a fluoropolymer.

To be useful, these multi-layer articles should not delaminate duringuse. That is, the adhesive bond strength between the layers of themulti-layer article should be sufficient to prevent the layers fromseparating. A variety of methods have been employed to increase the bondstrength between a layer comprising a fluoropolymer and a layercomprising a substantially non-fluorinated polymer. For example, a layerof adhesive can be added between the two layers. However, the adhesiveused must not limit the performance of the multi-layer article.

As an alternative to, or in addition to, adhesives, surface treatment ofone or both of the layers has been used to increase the adhesive bondstrength between the layers. For example, layers comprising afluoropolymer have been treated with a charged gaseous atmospherefollowed by application of a layer of thermoplastic polyamide. Suchsurface treatments add additional steps and cost to the manufacturingprocess and are limited to non-coextrusion processes.

In another approach, the adhesion between a substantiallynon-fluorinated polymer and a fluoropolymer, wherein the fluoropolymeris derived from vinylidene fluoride (VDF), and optionallyhexafluoropropylene (HFP), has been found to increase upon exposure ofthe fluoropolymer to an amine compound. An example includes providing afluoropolymer comprising interpolymerized units derived from vinylidenefluoride, a layer of a melt-processable, substantially non-fluorinatedpolymer, and a melt-processable aliphatic di- or polyamine of less than1,000 molecular weight. Unfortunately, fluoropolymer derived from VDFare relatively susceptible to chemical attack by basic materials, thusrendering them unacceptable in certain chemical applications.

In contrast, fluoropolymers derived from fluorinated monomers thatinclude substantially no VDF are known to be more chemically inert thanfluoropolymer derived from VDF monomers, and are more resistant tochemical attack. Thus, such fluoropolymers are ideal for use incomposite applications (e.g., articles having multi-layers) where a moreresistant barrier layer is desired, such as automotive hoseapplications. Such articles combine the chemical resistance of thefluoropolymer with the structural properties of a generally thicker andlower cost hydrocarbon material. Examples of such substantially non-VDFderived fluoropolymers include fluoropolymers derived from monomers oftetrafluoroethylene (TFE), hexafluoropropylene (HFP),chlorotrifluoroethylene (CTFE), and optional non-fluorinated monomers.The chemical resistance provided by these fluoropolymers make suchcomposite articles useful as automotive fuel lines, fuel tanks, otherelements of automobile systems, as well as liners, tubing and containersin chemical processing and any other use where chemically resistantbarriers are desired.

However, because of the improved chemical resistance of thesesubstantially non-VDF derived fluoropolymers, they are also less likelyto undergo adhesion-promoting reactions with amines. Although somedegree of adhesion may be obtained on exposure of a substantiallynon-VDF containing fluoropolymer to an amine, many applications willbenefit from, and may require, higher adhesion to a fluoropolymer thatprovides a chemically resistant barrier. Thus, poor adhesion between thenon-VDF containing fluoropolymer and a hydrocarbon material makesformation of useful composite articles difficult.

What is yet needed is a composite article that includes a barriercomprising a substantially non-vinylidene fluoride containing polymerthat adheres well to a substantially non-fluorinated polymericsubstrate.

SUMMARY OF THE INVENTION

In accordance with the invention, one embodiment is a composite articlecomprising: a blend component that has first and second surfaces, and asubstantially non-fluorinated polymer component adhered to the firstsurface of the blend component. The non-fluorinated polymer componenthas one or more pendant primary or secondary amine groups and providesan exposed surface. The blend component comprises (i) avinylidene-fluoride containing fluoropolymer and (ii) a firstsubstantially non-vinylidene fluoride containing fluoropolymer. As usedherein, the term “blend” means that the polymers are mixed together.These polymers can be mixed by any conventional method, includingsolution mixing, melt-mixing or dispersion mixing.

It was found that this embodiment of the invention improved the adhesionbetween a non-VDF containing fluoropolymer component and the componentconsisting of a substantially non-fluorinated polymer.

In another embodiment of the invention, a composite article includes asecond substantially non-fluorinated polymer component adhered to theexposed surface of the first substantially non-fluorinated polymercomponent.

In either of the embodiments above, the composite article may furtherinclude a component comprising a second substantially non-VDF containingfluoropolymer bonded to the second surface of the blend component.

In another embodiment of the invention, a multi-layer composite articleincludes in order, a first layer of a substantially non-VDF containingfluoropolymer; a second layer of a blend of a VDF containingfluoropolymer and a substantially non-vinylidene fluoride containingfluoropolymer, a third layer comprising a substantially non-fluorinatedpolymer having pendant amine groups, and a fourth layer comprising asubstantially non-fluorinated polymer.

Another embodiment of the invention includes a method for adhering afluorinated component to a substantially non-fluorinated component. Themethod comprises the steps of providing (A) the non-fluorinated polymer,(B) a blend of (i) a VDF containing fluoropolymer; and (ii) a firstsubstantially non-VDF containing fluoropolymer and (C) a substantiallynon-fluorinated polymer having one or more pendant primary or secondaryamine groups, and, sequentially or simultaneously,

-   -   adhering the blend component (B) to the pendant amine component        (C), and    -   adhering the non-fluorinated polymer component (A) to the        pendant amine component (C).

This method provides composite articles (e.g., multi-layer articles)having improved adhesive bond strength between a fluorinated componentand a substantially non-fluorinated component through the inclusion of afluoropolymer blend component. The composite article of the inventioncan be a shaped article, such as a sheet or film, a hose, a tube, a wirecoating, a cable jacket, and a container. The invention providescomposite articles suitable for use in motor vehicles, for example, asfuel-line hoses, chemical handling and processing, wire and cableapplications, sheets or films, blow-molded and extruded articles such asbottles, tubes, etc. The articles of the invention are especially usefulwhere chemical resistance and barrier properties are important.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

FIGS. 1-5 are cross-sectional views of various embodiments of thecomposite article of the invention;

FIG. 6 is a cross-sectional view of a layered construction used intesting adhesion of a composite article in accordance with theinvention.

The FIGS are not intended to limit the present invention. Consequently,it is understood that the specific constructions are illustrative only.In these several views, similar reference numbers refer to the sameelements.

DESCRIPTION OF PREFERRED EMBODIMENTS

The various embodiments of the invention utilize fluorinated polymers(also known as fluoropolymers). Fluoropolymers used in the inventioninclude vinylidene fluoride containing fluoropolymers and substantiallynon-vinylidene fluoride containing fluoropolymers. Additionally, thefluoropolymers used in the invention include both fluoroplastics (alsoknown as fluorothermoplastics) and fluoroelastomers.

Fluoroplastics are distinguished from fluoroelastomers or fluororubbersby their properties. Fluoroplastic materials are melt-processable andhave either a melt point and are semi-crystalline, or have a glasstransition temperature above ambient temperature. In contrast,fluoroelastomers or fluororubbers are generally amorphous and usually donot exhibit a melt point. While some fluoroelastomers may bemelt-processable, a curing step is typically used in making finishedarticles of fluoroelastomers. The curing step generally results in amaterial with substantially reduced melt-processability. The termsfluoroelastomer and fluororubber are generally used interchangeably.See, for example, American Society for Testing and Materials (ASTM) D1566 for elastomer and rubber definitions.

Vinylidene Fluoride Containing Fluoropolymers

As used herein the term “vinylidene fluoride containing fluoropolymer”includes fluoropolymers derived from vinylidene fluoride (“VF2” or“VDF”) and fluoropolymers derived from other monomers which, whenpolymerized, form monomer sequences similar to polymerized vinylidenefluoride. In general, these fluoropolymers will readilydehydrofluorinate when exposed to a base. As a result, suchfluoropolymers undergo relatively facile reactions with aminecomponents. These reactions can result in improved adhesion. These othersuch monomers include ethylenically unsaturated monomers which, whenincorporated into fluoropolymers, can produce a similar (including anidentical) polymeric microstructure as the polymerized VDF. Thesesimilarly formed polymers are also prone to dehydrofluorination and asubsequent adhesion promoting reaction with an amine. In general, themicrostructure of a carbon bonded hydrogen atom between carbon bondedfluorine atoms creates an amine reactive site. The reactivity of acarbon bonded hydrogen is further enhanced when its carbon atom isadjacent to, or attached to a carbon atom possessing a carbon bonded—CF3 group (supplied by HFP or 2-hydropentafluoropropylene for instance)or another electron withdrawing group. Monomers suitable for formingsuch carbon-bonded-hydrogen reactive sites include, but are not limitedto, VDF, 1-hydropentafluoropropene, 2-hydropentafluoropropene, andtrifluoroethylene.

Preferably, these VDF-containing fluoropolymers are easily prone todehydrofluorination and are also prone to a subsequent adhesionpromoting reaction with an amine. The carbon-bonded-hydrogen sitesproduced upon copolymerization of these monomers, including VDF, can bepredehydrofluorinated (prior to blend formation) to form double bondswithin the backbone of the fluoropolymer. While not wishing to be boundby any particular theory, it is believed that preformation of thesedouble bonds may accelerate the amine adhesion promoting reaction. Thisdehydrofluorination reaction may also be produced in situ, e.g., duringprocessing. This in situ dehydrofluorination reaction may be aided bythe use of an appropriate catalyst, preferably of the type discussedbelow. Such VDF-containing fluoropolymers comprises at least 3% byweight of interpolymerized units derived from VDF or other monomers withsimilar reactivity when polymerized. These VDF-containing fluoropolymersmay be homopolymers or copolymers with other ethylenically unsaturatedmonomers. More preferably, the VDF-containing fluoropolymer is formedfrom (i) a fluorine-containing monomer selected from the group ofvinylidene fluoride, trifluoroethylene, 1-hydropentafluoropropylene,2-hydropentafluoropropylene, mixture thereof, and optionally (ii) atleast one monomer copolymerizable therewith. In one preferredembodiment, the VDF-containing fluoropolymer comprises ahexafluoropropylene-vinylidene fluoride polymer.

Such VDF-containing fluoropolymers (homopolymers, copolymers,terpolymers, etc.) can be made by well-known conventional means, forexample by, free-radical polymerization of VDF with or without otherethylenically unsaturated monomers. The preparation of colloidal,aqueous dispersions of such polymers and copolymers is described, forexample, in U.S. Pat. No. 4,335,238 (Moore et al.). Customary processesfor making such amine-reactive fluoropolymers can include copolymerizingfluorinated olefins in aqueous, colloidal dispersions, which is carriedout in the presence of water-soluble initiators which produce freeradicals, such as, for example, ammonium or alkali metal persulfates oralkali metal permanganates, and in the presence of emulsifiers, such as,in particular, the ammonium or alkali metal salts of perfluorooctanoicacid.

These VDF-containing fluoropolymers useful in this invention canoptionally include other useful fluorine-containing monomers such ashexafluoropropene (HFP), tetrafluoroethylene (TFE),chlorotrifluoroethylene (CTFE), 2-chloropentafluoro-propene, afluorinated vinyl ether, including a perfluoroalkyl vinyl ether such asCF₃OCF═CF₂ or CF₃ CF₂ CF₂OCF═CF₂. Certain fluorine-containing di-olefinsare also useful, such as, perfluorodiallyether andperfluoro-1,3-butadiene.

The VDF-containing fluoropolymers useful in this invention may alsocomprise interpolymerized units derived from fluorine-free, unsaturatedolefin comonomers, e.g., ethylene, propylene or butadiene. Preferably,at least 50% by weight of all monomers in a polymerizable mixture arefluorine-containing. The VDF-containing fluorine-containing monomer mayalso be copolymerized with iodine- or bromine-containing unsaturatedolefin monomer. These monomers, sometimes referred to as cure-sitemonomers, are useful to prepare a peroxide curable polymer. Suitablecure-site monomers include terminally unsaturated monoolefins of 2 to 4carbon atoms such as bromodifluoroethylene, bromotrifluoroethylene,iodotrifluoroethylene, and 4-bromo-3,3,4,4-tetrafluoro-1-butene.

Useful commercially available VDF-containing fluoropolymer materialsinclude, for example, THV 200, THV 400, THV 500G fluoropolymer(available from Dyneon LLC, St. Paul, Minn.), KYNAR 740 fluoropolymer(available from Atochem North America, Philadelphia, Pa), HYLAR 700(available from Ausimont USA, Inc., Morristown, N.J.), and FLUORELFC-2178 (available from Dyneon LLC).

Substantially Non-vinylidene Fluoride Containing Fluoropolymers

These fluoropolymers typically do not contain VDF monomer (or any othersimilar monomer) at a level such that, when polymerized, produces amicrostructure which is readily susceptible to reaction with a base, asdescribed above. Hence, these fluoropolymers are referred to herein as“substantially non-vinylidene fluoride (non-VDF) containingfluoropolymers.” By “substantially non-VDF containing,” it is meant thatthe fluoropolymer preferably is substantially free from interpolymerizedunits derived from VDF monomer, or other monomers which provide amicrostructure similar to that described above. These fluoropolymerscomprise less than 3%, preferably less than 1% by weight ofinterpolymerized units derived from VDF or other monomers which producea microstructure similar to that described above.

Useful substantially non-VDF containing fluoropolymers include meltprocessable fluoroplastics formed from polymerizing one or morefluorine-containing monomers selected from the group of HFP, TFE, CTFE,and a fluorinated vinyl ether, and may optionally include one or morecure site monomers. Such cure site monomers are typically iodide- orbromide-containing unsaturated olefins. Preferably the cure sitemonomers are terminally unsaturated monoolefins that contain from 2 to 4carbon atoms. Examples of useful cure site monomers includebromodifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene,4-bromo-3,3,4,4-tetrafluorobutene-1, and mixture thereof. Particularlyuseful fluorine-containing monomers are HFP, TFE, and CTFE.

The fluorine-containing monomer used to make the non-VDF containingfluoropolymer may also be copolymerized with fluorine-free unsaturatedolefin comonomers, e.g., ethylene, propylene or butadiene. Certainfluorine-containing diolefins are also useful, such asperfluorodiallyether and perfluoro-1,3-butadiene. Preferably at least50% by weight of all monomers in a polymerizable mixture arefluorine-containing.

Additional examples of fluoroplastics useful in the invention aresubstantially non-VDF containing copolymers of substantially fluorinatedand substantially non-fluorinated olefins. One of these substantiallynon-VDF containing copolymers is a terpolymer containing TFE, HFP andethylene. For instance, a useful copolymer contains about 45 mol % toabout 75 mol % of TFE units, about 10 mol % to about 30 mol % of HFPunits, and about 10 mol % to about 40 mol % of ethylene units and has amelting point of about 140° C. to about 250° C.

Another example of a useful fluoroplastic in the present inventioncomprises interpolymerized units derived from TFE and allylichydrogen-containing olefin monomer. International Publication No. WO96/18665 (Greuel) describes fluoropolymers and preferred methods ofproducing interpolymerized units derived from TFE and polypropylene. Thecopolymers can generally contain, e.g., from about 2 weight percent toabout 20 weight percent (preferably from about 5 weight percent to about15 weight percent, more preferably from about 7 weight percent to about12 weight percent) allylic hydrogen-containing olefin monomer. Thesesemi-crystalline copolymers typically have melt temperatures so thatthey can be processed at temperatures below about 300° C., preferablyfrom about 200° C. to about 250° C.

Examples of useful substantially non-VDF containing fluoropolymers ofthis type include poly(ethylene-co-tetrafluoroethylene),poly(tetrafluoroethylene-co-propylene),poly(chlorotrifluoroethylene-co-ethylene), and the terpolymerpoly(ethylene-co-tetrafluoroethylene-co-hexafluoropropylene), as well asperfluorinated melt processable plastics, among others. Also, manyuseful substantially non-VDF containing fluoropolymer materials arecommercially available, for example from Dyneon, LLC, St. Paul, Minn.,under the trade designations X6810, and X6820, from Daikin America,Inc., Dacatur, Ala., under the trade designations NEOFLON EP-541,EP-521, and EP-610, from Asahi Glass Co., Tokyo, Japan, under the tradedesignations AFLON COP C55A, C55AX, C88A, and from DuPont, Wilmington,Del., under the trade designations TEFZEL 230 and 290.

Many ways to make such polymers (including copolymers, terpolymers,etc.) are known. Such methods include, but are not limited to,suspension free-radical polymerization or conventional emulsion, whichtypically involve polymerizing monomers in an aqueous medium in thepresence of an inorganic free-radical initiator system and surfactant orsuspending agent. In general, the desired olefinic monomers can becopolymerized in an aqueous colloidal dispersion in the presence ofwater-soluble initiators which produce free radicals such as, forexample, ammonium or alkali metal persulfates or alkali metalpermanganates, and in the presence of emulsifiers such as, inparticular, ammonium or alkali metal salts of perfluorooctanoic acid.See, for example, U.S. Pat. No. 4,335,238.

The substantially non-VDF containing fluoropolymers are comprised ofessentially fluorinated and essentially non-fluorinated olefins. Theycan be prepared using a fluorinated sulfinate as a reducing agent and awater soluble oxidizing agent capable of converting the sulfinate to asulfonyl radical. Preferred oxidizing agents are sodium, potassium, andammonium persulfates, perphosphates, perborates, and percarbonates.Particularly preferred oxidizing agents are sodium, potassium, andammonium persulfates.

Aqueous emulsion and suspension polymerizations can be carried out inconventional steady-state conditions in which, for example, monomers,water, surfactants, buffers and catalysts are fed continuously to astirred reactor under optimum pressure and temperature conditions whilethe resulting emulsion or suspension is removed continuously. Analternative technique is batch or semibatch polymerization by feedingthe ingredients into to stirred reactor and allowing them to react at aset temperature for a specified length of time or by chargingingredients into the reactor and feeding the monomer into the reactor tomaintain a constant pressure until a desired amount of polymer isformed.

Blend Component

The blend component used in the invention includes the VDF containingfluoropolymer and a substantially non-VDF containing fluoropolymer, eachdescribed above. The blend component includes the VDF-containingfluoropolymer in an amount from preferably about 5 wt. %, to about 75wt. %, and more preferably about 10 wt. % to preferably about 50 wt. %.The blend component also includes the substantially non-VDF containingfluoropolymer in an amount from preferably about 25 wt. %, to about 95wt. %, and more preferably about 50 wt. % to about 90 wt. %.

Blends of the VDF-containing fluoropolymer and the substantially non-VDFcontaining fluoropolymer may be formed by a variety of known techniques.These include melt mixing these fluoropolymers either by a batch mixingtechnique or a continuous extrusion process. Mixing and coating offluoropolymer dispersions, followed by thermal annealing, may also beused to form the blend component. Of course, material selection andchoice of process may be determined by the end use requirements as wellas melt viscosity ratios between the components.

When employing the blend component in the composite article, increasedadhesion is observed by a greater peel strength value between the blendcomponent and the component including a substantially non-fluorinatedpolymer containing pendant amine groups when compared to a peel strengthvalue between a component consisting of a substantially non-VDFcontaining fluoropolymer and a component consisting of a substantiallynon-fluorinated polymer having pendant amine groups. This isparticularly significant in applications where long durability of acomposite article is required, such as in automobile fuel line where afuel hose is continually exposed to petrochemicals (e.g., fuel).

Substantially Non-Fluorinated Polymers

It is contemplated that the invention may also include a substantiallynon-fluorinated thermoplastic or elastomeric polymer component bonded tothe component comprising a polymer having pendant amine groups.Typically, this is opposite the blend component. The substantiallynon-fluorinated polymer component can provide added structural integrityand reduced cost, among other things.

Useful substantially non-fluorinated materials can include any of anumber of well known, substantially non-fluorinated polymers. As usedherein the term “substantially non-fluorinated” refers to polymers andpolymeric materials having fewer than 10 percent of their carbon-bondedhydrogen atoms replaced with fluorine atoms. Preferably, thesubstantially non-fluorinated polymer has fewer than 2 percent of itscarbon-bonded hydrogen atoms replaced with fluorine atoms, and morepreferably fewer than 1 percent of its carbon-bonded hydrogen atoms arereplaced with fluorine atoms.

Preferred substantially non-fluorinated polymers include thermoplasticpolymers such as polyamides, polyimides, polyurethanes, polyolefins,polystyrenes, polyesters, polycarbonates, polyketones, polyureas,polyacrylates and polymethacrylates. The particular substantiallynon-fluorinated polymer selected will depend upon the application ordesired properties.

Polyamides useful as the substantially non-fluorinated polymer aregenerally commercially available. For example, polyamides such as any ofthe well-known nylons are available from a number of sources.Particularly preferred polyamides are nylon-6, nylon-6,6, nylon-11, ornylon-12. It should be noted that the selection of a particularpolyamide material should be based upon the physical requirements of theparticular application for the resulting article. For example, nylon-6and nylon-6,6 offer higher heat resistant properties than nylon-11 ornylon-12, whereas nylon-11 and nylon-12 offer better chemical resistantproperties. In addition to those polyamide materials, other nylonmaterials such as nylon-6,12, nylon-6,9, nylon-4, nylon-4,2, nylon-4,6,nylon-7, and nylon-8 may also be used. Ring containing polyamides, e.g.,nylon-6, T and nylon-6,1, may also be used. Polyether containingpolyamides, such as PEBAX polyamides (Atochem North America,Philadelphia, Pa.), may also be used.

Useful polyurethane polymers include aliphatic, cycloaliphatic,aromatic, and polycyclic polyurethanes. These polyurethanes aretypically produced by reaction of a polyfunctional isocyanate with apolyol according to well known reaction mechanisms. Useful diisocyanatesfor employment in the production of a polyurethane includedicyclohexylmethane4,4′-diisocyanate, isophorone diisocyanate,1,6-hexamethylene diisocyanate, cyclohexyl diisocyanate, anddiphenylmethane diisocyanate. Combinations of one or more polyfunctionalisocyanates may also be used. Useful polyols includepolypentyleneadipate glycol, polyetramethylene ether glycol,polyethylene glycol, polycaprolactone diol, poly-1,2-butylene oxideglycol, and combinations thereof. Chain extenders, such as butanediol orhexanediol, may also optionally be used in the reaction. Commerciallyavailable urethane polymers useful in the present invention include:PN-3429 from Morton International, Inc., Seabrook, N.H., and X-4107 fromB.F. Goodrich Company, Cleveland, Ohio.

The polyolefin polymers useful as the substantially non-fluorinatedpolymer are generally homopolymers or copolymers of ethylene, propylene,acrylic monomers, or other ethylenically unsaturated monomers, forexample, vinyl acetate and higher alpha-olefins. Such polymers andcopolymers can be prepared by conventional free-radial polymerization orcatalysis of such ethylenically unsaturated monomers. The degree ofcrystallinity of the hydrocarbon polymer or copolymer can vary. Thepolymer may, for example, be a semi-crystalline high densitypolyethylene or may be an elastomeric copolymer of ethylene andpropylene. Carboxyl, anhydride, or imide functionalities may beincorporated into the hydrocarbon polymer within the present invention,by polymerizing or copolymerizing functional monomers, for example,acrylic acid or maleic anhydride, or by modifying a polymer afterpolymerization, for example, by grafting, by oxidation or by formingionomers. These include, for example, acid modified ethylene vinylacetates, acid modified ethylene acrylates, anhydride modified ethyleneacrylates, anhydride modified ethylene vinyl acetates, anhydridemodified polyethylenes, and anhydride modified polypropylenes. Thecarboxyl, anhydride, or imide functional polymers useful as thehydrocarbon polymer are generally commercially available. For example,anhydride modified polyethylenes are commercially available from DuPont,Wilmington, Del., under the trade designation BYNEL coextrudableadhesive resins.

Polyacrylates and polymethacrylates useful as the substantiallynon-fluorinated polymer include, for example, polymers of acrylic acid,methyl acrylate, ethyl acrylate, acrylamide, methylacrylic acid, methylmethacrylate, and ethyl acrylate, to name a few. As mentioned above,other useful substantially non-fluorinated polymers include polyesters,polycarbonates, polyketones, and polyureas. These materials aregenerally commercially available, for example, SELAR polyester (DuPont,Wilmington, Del.), LEXAN polycarbonates (General Electric, Pittsfield,Mass.), KADEL polyketone (Amoco, Chicago, Ill.), and SPECTRIM polyurea(Dow Chemical, Midland, Mich.),

Preferred substantially non-fluorinated elastomer polymers includeacrylonitrile butadiene (NBR), butadiene rubber, chlorinated andchloro-suflonated polyethylene, chloroprene, EPM EPDM, epichiorohydrin(ECO), isobutylene isoprene, isoprene, polysulfide, polyurethane,silicone, PVC-NBR, styrene butadiene, and vinyl acetate ethylene.Examples of these compounds include Nipol 1052 NBR (Zeon, Louisville,Ky.), Hydrin 2000 ECO (Zeon, Louisville, Ky.), Hypalon 48 (Dupont,Wilmington, Del.), and Nordel 2760P EPDM (Dupont, Wilmington Del.).

Substantially Non-Fluorinated Polymers having Pendant Amine Groups

Useful substantially non-fluorinated polymers having pendant aminegroups preferably include any of the substantially non-fluorinatedpolymers described above so long as a pendant amine group is provided.More preferably, these non-fluorinated polymers having pendant aminegroups contain one or more primary amine groups. For example, aliphaticdi-, or polyamines mixed and reacted with a substantiallynon-fluorinated polymeric material described above can be used in acomposite article according to the invention. The term “di-, orpolyamines” as used within this description refers to organic compoundcontaining at least two amine groups. By “aliphatic” it is meant thatthe nitrogen atoms of at least two of the two or more amines in thecompound are bonded directly to only hydrogen atoms or aliphatic carbonatoms rather than being bonded directly to aromatic moieties orfunctional groups (e.g., carboxyl). For example, as “aliphatic di-, orpolyamine” is used within the present description, aniline and urea arenot aliphatic di-, or polyamines. Secondary amines are more preferredthan tertiary amines and primary amines are most preferred. These aminesmodify a substantially non-fluorinated polymer which makes up thecomponent of the composite article to which the blend is adhered.

Primary-amine containing polymers are obtained, for example, by reactingcarboxyl-containing hydrocarbon elastomers with diamines, for example,2-methylpentanediamine and N-aminoethylpiperazine. Most preferred arealkylene polyamines or diamines that comprise at least two primaryamines, such as hexamethylene diamine, dodecyl diamine, and2,4,8,10-tetraoxaspiro[5,5]undecane-3,9-dipropanamine. Such polymers andcopolymers can be prepared by free radical polymerization ofethylenically unsaturated monomers.

A particularly useful non-fluorinated polymer (polyamide) having pendantamine groups is commercially available under the trade designationGRILAMID FE4943, now known as GRILAMID XE3595 and GRILAMID FE5405, bothavailable from EMS Chemie AG (Switzerland). Other materials which may bemodified with the addition of pendant amine groups include polyimides,polyesters, polycarbonates, polyketones, and polyureas. These materialsare generally commercially available, for example, SELAR polyester fromDuPont (Wilmington, Del.), LEXAN polycarbonate (General Electric,Pittsfield, Mass.), KADEL polyketone (Amoco, Chicago, Ill.), andSPECTRIM polyurea (Dow Chemical, Midland, Mich.).

Catalysts

In addition to pendant amine functionality, other catalyst systems maybe added to the amine functionalized substantially non-fluorinatedpolymer component to accelerate bonding to the fluoropolymer blendcomponent. Certain catalysts may also be added to the blend componentprovided that they are not overly reactive with the blend component.These catalysts may include oregano-onium compounds used in conjunctionwith an acid acceptor.

Many of the oregano-onium compounds useful in this invention aredescribed in the art and contain at least one heteroatom (i.e., anon-carbon atom such as N, P, S, O) bonded to organic or inorganicmoieties. See, for example, U.S. Pat. No. 4,882,390 (Grootaert et al.);U.S. Pat. No. 3,655,727 (Patel et al.); U.S. Pat. No. 3,712,877 (Patelet al.); U.S. Pat. No. 3,857,807 (Kometani): U.S. Pat. No. 3,686,143(Bowman); U.S. Pat. No. 3,933,732 (Schmiegel); U.S. Pat. No. 3,876,654(Pattison); U.S. Pat. No. 4,233,421 (Worm); U.S. Pat. No. 4,259,463(Moggi et al.); U.S. Pat. No. 4,673,715 (Caywood): U.S. Pat. No.4,833,212 (Yamada et al.); U.S. Pat. No. 4,748,208 (Kasahara et al.);U.S. Pat. No. 4,501,858 (Moggi); U.S. Pat. No. 4,882,390; and also seeWest, A. C. and Holcomb, A. G. “Fluorinated Elastomers”, Kirk-Othmer;Encyclopedia of Chemical Technolog, Vol. 8, 3^(rd) Ed., John Wiley &Sons, Inc., pp. 500-515 (1979). Mixtures of oregano-onium compounds arealso useful in this invention.

Preferably, the oregano-onium compounds include quaternary oregano-oniumcompounds (such as those selected from the group consisting of ammonium,arsonium, phosphonium, stibonium, amino-phosphonium, phosphorane andimmium compounds) and sulfonium compounds. Many of such compounds aredescribed in U.S. Pat. No. 4,882,390 (Grootaert et al.).

Representative oregano-onium compounds useful in this invention include:

tetrabutylammonium chloride, tetrabutylammonium bromide,tetrahexylammonium chloride, tetraheptylammonium chloride,triphenylben-zylphosphonium chloride, tetrapentylammonium chloride,tributylallylphosphonium chloride, tributylbenzylphosphonium chloride,dibutyldiphyneylphosphonium chloride, tetrabutylphosphonium chloride andtributyl(2-methoxy)propylphosphonium chloride, phenyltrimethylammoniumchloride, tetrapropylammonium bromide, tetraheptylammonium bromide,tetramethylphosphonium chloride, tetramethylammonium chloride,tetraphenylphosponium chloride, tetraphenylarsonium chloride,tetraphenylstibonium chloride, benzyltris (dimethylamino) phoisphoniumchloride, bis (benzyldiphenylphosphine) iminium chloride compounds andmixtures thereof.

Acid acceptors can be inorganic or organic compounds. Organic acidacceptors include sodium stearate, magnesium oxalate, andbenzotriazoate. However, acid acceptors are generally inorganic basesand include magnesium oxide, lead oxide, calcium oxide, calciumhydroxide, dibasic lead phosphite, zinc oxide, barium carbonate,strontium hydroxide, calcium carbonate, etc.

The catalysts may also include amine compounds other than the pendantamine used in the substantially non-fluorinated polymer having pendantamine groups. Representative classes of useful amine compounds includealiphatic, aryl and amidine amine compounds. Preferably the aminecompound is a secondary or tertiary amine compound. Examples of theseinclude 4-dimethyl amino pyridine, triisooctyl amine,1,8-diazobicyclo(2,2,2)-octane, 1,5-diazobicyclo[4.3.0] non-5-ene, and1,8-diazobicyclo[5.4.0]undec-7-ene, imidazole, benzotriazole, to name afew.

A useful class of amine compounds can be represented by the followingformula:

where:

-   -   R¹ is independently selected from substituted and unsubstituted        alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups;    -   R² is independently selected from H, and substituted and        unsubstituted alkyl, cycloalkyl, aryl, aralkyl and alkaryl        groups;    -   R³ is selected from substituted or unsubstituted alkylene,        cycloalkylene, arylene, aralkylene, and alkarylene groups; n is        a number from 0 to about 100.

The catalyst may be incorporated into either the blend component or thependant amine-containing non-fluorinated polymer component. Preferablyit is incorporated into the latter.

Optional Additives

The composite articles in accordance with the invention may also includeoptional additives, such as those typically used in other thermoplasticapplications. The optional additives are preferably selected from thegroup of a polymer, a pigment, a tackifier, a filler, electricallyconductive materials (such as those described in U.S. Pat. No.5,552,199), electrically insulative materials, a stabilizer, anantioxidant, a lubricant, a processing aid, an impact modifier, aviscosity modifier, and mixtures thereof.

Discussion of the Drawings

The present invention, and the orientation of the previously describedcomponents within those components, will be further understood byreference to the FIGURES.

Referring first to FIG. 1, a cross-sectional view is shown of a sectionof a two component construction 10 according to the invention. Thisembodiment may comprise a film, a sheet, a tube, a wire coating, a cablejacket, a container wall, etc. Construction 10 comprises a first layer12 having first and second surfaces 14 and 16 respectively, and a secondlayer 18 bonded to first surface 14.

First layer 12 comprises the blend component of the VDF-containingfluoropolymer and the substantially non-VDF containing fluoropolymer.The blend layer 12 is advantageous because it can provide a chemicalbarrier to the construction 10. Second layer 18 comprises thesubstantially non-fluorinated polymer having pendant amine groups.

Referring now to FIG. 2, a three layer construction according to theinvention is generally shown as a cross-sectional view of a tubing or ahose segment 20. The first, or outer layer or wall 22 providesstructural integrity to the composite article and is made from asubstantially non-fluorinated polymer. An intermediate layer 24 providesadhesion between outer layer 22 and an inner layer 26. The intermediatelayer 24 comprises a substantially non-fluorinated polymer havingpendant amine groups. The inner layer 26 comprises the blend ofVDF-containing fluoropolymer and the first substantially non-vinylidenefluoride containing fluoropolymer. The inner (or blend) layer 26 isadvantageous because it can provide a sufficient barrier for thecomposite article 20. In this embodiment, blend layer 26 faces cavity 28which provides the passageway for the chemical desired in the intendeduse of the composite article, such as fuel or vapor lines in anautomobile fuel system.

Referring now to FIG. 3, this three layer construction according to theinvention comprises an outer layer 32, an intermediate layer 34 and aninner layer 36. Outer layer 32 comprises the substantiallynon-fluorinated polymer having pendant amine groups. The intermediatelayer 34 comprises the blend of the VDF containing fluoropolymer and thenon-VDF containing fluoropolymer. The inner layer 36 provides chemicaland/or flame barrier to the composite article 30 and comprises thesubstantially non-VDF containing fluoropolymer. The composite article 30may also be provided as a flat sheet that can be used as gaskets, seals,diaphragms, and molded articles such as containers, liners, and thelike.

FIG. 4 illustrates a four layer embodiment of the invention.Construction 40 is generally shown as a cross-section of a tube or ahose segment, although it may also be employed in any of the other usesencompassed by this specification. Construction 40 generally comprisesouter layer 42, first intermediate layer 44, second intermediate layer46, and inner layer 48. Outer layer 42 comprises the substantiallynon-fluorinated polymer; first inner layer 44 the substantiallynon-fluorinated polymer having pendant amine groups; second inner layer46 the blend component; and inner layer 48 the substantially non-VDFcontaining fluoropolymer.

Referring to FIG. 5, another preferred embodiment of the invention is acomposite article generally shown as a cross-sectional view of a coatedwire/cable 50. The coated wire or cable comprises an optional outerlayer 52 of a substantially non-VDF containing fluoropolymer thatprovides a barrier, e.g., the chemical resistance and/or electricalinsulating properties to the composite article; first intermediate layer54 of the blend component; a second intermediate layer 56 of thesubstantially non-fluorinated polymer having pendant amine groups; andan optional inner layer 58 of the substantially non-fluorinatedfluoropolymer.

In the constructions of FIGS. 3-5, the peel strength between the blendlayer (layers 34, 46, and 54 respectively) and the layer of the aminemodified polymer (layers 32, 44, and 56 respectively) is greater thanthe peel strength that would exist between the layer of non-VDFcontaining fluoropolymer (layer 36, 48, and 52 respectively) and thelayer of the amine modified polymer (layers 32, 44, and 56 respectively)if they were bonded directly to each other and tested under the sameconditions.

In any of these embodiments, the substantially non-VDF containingfluoropolymer used in the blend layer and the fluoropolymer used in thelayer providing the barrier can be the same or different substantiallynon-VDF containing polymer, such as those described previously.Preferably, the non-VDF containing fluoropolymers are compatible withone another. Most preferably, they are the same or similar.

In any of the embodiments of the invention, the various layers arebonded to the adjacent layer or layers. Preferably they are intimatelybonded to the adjacent layer or layers. As used herein, the term“intimately bonded” means that the components or layers are not easilyphysically separated without substantially destroying the composite ormulti-layer article. Additionally, any of the embodiments contemplatedby the invention can be provided in the form of a sheet or filmregardless of the specific embodiment illustrated in the FIGS. Further,the order of the layer may be reversed in any of these embodiments.Determination of what comprises the inner and outer layers is influencedby where the barrier properties are desired.

Composite Article Formation

Methods known in the polymer art can be used to produce a compositearticle, such as a bonded multi-layer article, wherein the fluoropolymerblend component is in substantial, preferably intimate, contact with thesubstantially non-fluorinated polymeric material having pendant aminegroups. For instance, the fluoropolymer blend component and thesubstantially non-fluorinated polymeric material having pendant aminegroups can be formed by known methods into thin films or thicker sheets.These films or sheets can be laminated together under heat and/orpressure to form a bonded multilayer article. Alternatively, thefluoropolymer blend component and the substantially non-fluorinatedpolymer having pendant amine groups can be simultaneously co-extrudedinto a multi-layer article.

The formulation of the fluoropolymer blend component may also beaccomplished during the formulation of the composite article. Forinstance, the non-vinylidene fluoride containing fluoropolymer and theVDF-containing fluoropolymer may be fed to and melt mixed by the sameextruder being employed during the co-extrusion process.

In addition, all of these methods can be used to apply additionalpolymeric components or layers either before, during, or after theformation of the fluoropolymer blend component in contact with thecomponent including the substantially non-fluorinated polymer havingpendant amine groups. For instance, a component including asubstantially non-vinylidene fluoride containing fluoropolymer can beapplied to the fluoropolymer blend component and then a componentincluding the substantially non-fluorinated polymer having pendant aminegroups can be applied to the fluoropolymer blend layer opposite thecomponent including a substantially non-vinylidene fluoride containingfluoropolymer. An optional component including a substantiallynon-fluorinated polymer can be applied adjacent to the componentincluding the substantially non-fluorinated polymer having pendant aminegroups opposite the blend component.

Conditions by which two or more components are brought together (e.g.,sequential extrusion, co-extrusion or lamination, to name a few) may besufficient to provide adequate adhesion between the components. However,it may be desirable to further treat the resulting composite articlewith, for example, heat and/or pressure to improve adhesion. One way tosupply additional heat, for example, is to slow the rate of coolingafter extrusion of the components. Also, additional heat or energy canbe added during or after extrusion or lamination processes, wherein thetemperatures may be higher than that required for merely processing thecomponents. Further, the complete composite article may be held at anelevated temperature and/or pressure for an extended period of time,such as in an oven, an autoclave, a heated liquid path and the like. Acombination of these methods can also be used.

The many advantages of a composite article in accordance with theinvention are further illustrated in the following non-limiting examplesin which all parts and percentages are given as parts and percentages byweight unless otherwise stated.

EXAMPLES

In the following Examples and Comparative Examples, various compositeswere prepared and the adhesion between the components, or layers, wasevaluated.

The abbreviations for the materials used are defined according to thefollowing schedule shown in Table 1.

TABLE 1 Abbreviation Description VDFP a terpolymer oftetrafluoroethylene, (VDF-containing hexafluoropropylene, andvinylidene, fluoropolymer) fluoride, commercially available from DyneonLLC, St. Paul, MN, under the trade designation THV 50OG PA an aminependant polyamide 12, (substantially commercially available from EMSChemie non-fluorinated polymer AG, Switzerland, under the trade havingpendant amine designation GRILAMD FE 4943 groups) NF polyamide 12,commercially available (substantially from Huls America, Piscataway, NJunder non-fluorinated polymer) the trade designation Vestamid ™ FEP afilm made from perfluorinated ethylene- propylene, commerciallyavailable from DuPont POLYMER 1 a terpolymer of ethylene,tetrafluoroethylene and hexafluoropropylene, commercially available fromDyneon LLC, St. Paul, MN, under the trade designation X6820 POLYMER 291% tetrafluoroethylene (TFE)-9% propylene (P) (percent by weight);T_(m) of 205° C.

POLYMER 2 was prepared by the method described in InternationalPublication No. WO 96/18665 (Greuel). In particular, a 150 L verticallystirred polymerization reactor was charged with 120,000 g deionizedwater, 70 g KOH, 430 g K₂HPO₄, 694 g ammonium perfluorooctanoate, 1,023g of a 20% solution of C₄F₉SO₂Na in deionized water. The reactor wasthen alternately evacuated and purged with N₂ until the level of 0₂ wasless than about 50 ppm. The reactor was then evacuated, the temperatureraised to about 71° C., and the agitation speed set about 210 rpm. Next,the reactor was charged with about 3929 g of TFE and about 79 g ofpropylene to give a pressure of about 15.2 bar (220 psig). Thepolymerization was initiated by feeding a 5% solution of (NH₄)₂S₂O₈ indeionized water to the reactor by means of a metering pump atapproximately 25 g/minute until 1 equivalent of(NH₄)₂S₂O₈ was fed(about3,200 g of solution). Upon the observation of a pressure drop, therunning feed, which consisted of 91% TFE and 9% propylene, was startedand continuously adjusted by the reactor's control system in order tomaintain the desired pressure. The polymerization was halted by allowingagitation after 31,300 g of TFE and 3,080 g of propylene has been fed, 5hours after start of running feed to give a calculated average reactionrate of 57 g/L-h. The reactor was then vented, cooled, and drained toisolate the latex. The resulting polymer was coagulated by adding HCl tothe latex, granulated, washed six times with deionized water, and driedovernight in an oven at about 120° C.

Example 1

In Example 1, 30 g of POLYMER 1 and 10 g of VDFP were blended using aRHEOMIX 600 internal bowl mixture equipped with roller blades, availablefrom Haake Buchler Instruments Inc., set at a temperature of 230° C. anda mixer rotor setting of 50 rpm. The pellets of the two components wereadded to the mixing bowl and blended for ten minutes. The internal-bowlmixed compound, i.e., the blend, was then removed from the mixer andmolded at 230° C. into a sheet approximately 0.0254 cm thick using a0.0254 cm shim stock and a Wabash Hydraulic Press Co. heated platenpress.

A composite was made with 1.25 cm by 5.0 cm samples of the blend sheetand a 2.54 cm by 7.62 cm by a 0.038 cm thick extruded sheet ofPOLYMER 1. A 1.25 cm by 5.0 cm by 0.0254 cm thick sheet of PA was placedon the other side of the blend sheet. Finally, a sheet of 2.54 cm×7.62cm by 0.038 cm thick sheet of NF was placed next to the PA layer given afinal structure of a layer of NF, a layer of PA, a layer of the blend,and finally a layer of POLYMER 1. Referring to FIG. 6, a layeredconstruction 60 used in testing layer adhesion is shown. The POLYMER 1layer 66 and the NF layer 68 extended beyond the blend layer 62 and thePA layer 64 for testing purposes.

The adhesion between the layers was tested using ASTM D-1876, commonlyknown as a “T-peel” test. To facilitate testing via the T-peel test, asheet of 0.00762 cm thick FEP film was placed between the POLYMER 1layer 66 and the NF layer 68 along the edges of the shorter edges of theblend layer 62 and the amine modified polyamide layer 64 as thecomposite was pressed and heated. The FEP film did not adhere to eitherthe POLYMER 1 layer 66and the NF layer 68 and was used only to create aPOLYMER 1 “tab” and a NF “tab” to insert into the jaws of the testdevice.

Three identical composites were simultaneously heated under pressureusing a Wabash Hydraulic Press Co. heated platen press at 230° C. and686 kPa for 3 minutes. The samples were removed from the press andallowed to cool to room temperature. Peel strength or adhesion wasmeasured on the samples in accordance with ASTM D 1876 (T-Peel test). AnINSTRON Model 1125 tester, available from Instron Corp., set at a 100mm/minute crosshead speed was used as the test drive. The peel strengthwas calculated as the average load measured during the peel test.

Comparative Example C1

In Comparative Example C1 a composite sample was prepared and tested asin Example 1, except that no PA layer was included between the blendlayer and the NF layer.

Comparative Example C2

In Comparative Example C2 a composite sample was prepared and tested asin Example 1, except that no blend layer was used between the POLYMER 1and the PA layer.

Examples 2 and 3 were done to evaluate a composite article of theinvention where the dehydrofluorination of the VDF polymer included acatalyst.

Example 2

In Example 2, 40 g of PA was further modified by the addition of 0.4 gof Dynamar™ FM 5166 catalyst, available from Dyncon LLC (St. Paul,Minn.), and 0.4 g calcium hydroxide powder using a RHEOMIX 600 internalblow mixer equipped with roller blades, available from Haake BuchlerInstruments Inc., set at a temperature of 200° C. and a mixer rotorsetting of 50 rpm. The PA pellets were first melted in the mixing bowlfor approximately one minute followed by the phase transfer catalyst andcalcium hydroxide, and the entire composition was mixed for anadditional five minutes. The internal-bowl mixed catalyzed compound wasthen removed from the mixer and molded at 230° C. into a sheetapproximately 0.0254 cm thick using a 0.0254 cm shim stock and a WabashHydraulic Press Co. heated platen press. After cooling, a composite wasprepared and tested as in Example 1 except the PA layer was replaced bya 1.25 cm by 5.04 cm sheet of the above described internal-blow mixedcatalyzed compound containing the phosphonium calcium hydroxidecatalysts.

Example 3

In Example 3, 40 g of PA was further modified by the addition of 0.2 gof 4-dimethyl amino pyridine (DMAP), available from Aldrich ChemicalCo., Milwaukee, Wis., using a RHEOMIX 600 internal bowl mixer equippedwith roller blades, available from Haake Buchler Instruments Inc., setat a temperature of 200° C. and a mixer rotor setting of 50 rpm. The PApellets were first melted in the mixing bowl for approximately oneminute followed by the DMAP, and the entire composition was mixed for anadditional five minutes. The blend was then removed from the mixer andmolded at 230° C. into a sheet approximately 0.0254 cm thick using a0.0254 cm shim stock and a Wabash Hydraulic Press Co. heated platenpress. After cooling, a composite was prepared and tested as in Example1 except the PA layer was replaced by a 1.25 cm by 5.04 cm sheet of theabove described internal-blow mixed catalyzed compound containing theDMAP catalyst.

Example 4

In Example 4, samples were prepared and tested as in Example 1, exceptthat the blend consisted of 36 g POLYMER 1 and 4 g VDFP.

Example 5

In Example 5, samples were prepared and tested as in Example 1, exceptthat the blend consisted of 20 g POLYMER 1 and 20 g VDFP.

Example 6

In Example 6, samples were prepared and tested as in Example 1, exceptthat the blend consisted of 10 g of POLYMER 1 and 30 g VDFP.

The tests results of Examples 1-6 and C1-C2 are set out in Table 2.

TABLE 2 Peel Strength Value Example (Kg/2.54 cm) Interface Failure 128.3 NF layer cohesive failure 1 13.6 blend/PA layers 2 18.1 blend/PAlayers 3 13.0 blend/PA layers 4 15.8 blend/PA layers 5 11.4 blend/PAlayers 6 1.3 blend/PA layers C1 5.9 blend/PA layers C2 POLYMER 1/PAlayers

Example 7

In Example 7, 30 g of POLYMER 2 and 10 g of VDFP were blended usingRHEOMIX 600 internal bowl mixer equipped with roller blades, availablefrom Haake Buchler Instruments Inc., set at a temperature of 230° C. anda mixer rotor setting of 50 rpm. The pellets of the two components wereadded to the mixing bowl and blended for ten minutes. The blend was thenremoved from the mixer and molded at 230° C. into a sheet approximately0.0254 cm thick using a 0.0254 cm shim stock and a Wabash HydraulicPress Co. heated platen press.

A composite was made with 1.25 cm by 5.08 cm samples of the blend filmand a 2.54 cm by 7.62 cm by 0.038 cm thick sheet of POLYMER 2. A 1.25 cmby 5.0 cm by 0.0254 cm thick sheet of PA, was placed on the other sideof the blend sheet. Finally, a sheet of 2.54 cm×7.62 cm by 0.0381 cmthick NF was placed adjacent to the PA sheet, giving a final structureof a layer of NF, a layer of PA, a layer of blend, and finally the layerof POLYMER 2. This layered construction was similar to that shown inFIG. 5, except that layer 80 was POLYMER 2.

Comparative Example 3

In Comparative Example 3, a sample was prepared as in Example 7, exceptthat no POLYMER 2-VDFP fluoropolymer blend layer was used.

All Examples and Comparative Examples were tested as explained inExample 1 above. Results are reposted in Table 1. Peel Strength Valuesare shown and the layer interface which separated during testing is alsoreported.

The test results of Examples 7 and C3 are shown in Table 3.

TABLE 3 Peel Strength Value Example (Kg/2.54 cm) Interface Failure 7 1.5blend/PA layers C3 0.2 POLYMER 2/PA layers

It is evident from the above examples and comparative examples that acomposition consisting of a blend of substantially non-VDF containingfluoropolymer and a VDF containing fluoropolymer may be used to giveimproved adhesion of the substantially non-VDF containing fluoropolymerto a pendant amine containing non-fluorinated polymeric material.

The complete disclosures of all patents, patent applications, andpublications are incorporated herein by reference as if individuallyincorporated. Various modifications and alterations of this inventionwill become apparent to those skilled in the art without departing fromthe scope and spirit of this invention, and it should be understood thatthis invention is not to be unduly limited to the illustrativeembodiments set forth herein.

1. A composite article comprising: (a) a blend component having firstand second surfaces, the blend component comprising: (i) a vinylidenefluoride containing fluoropolymer; and (ii) a substantiallynon-vinylidene fluoride containing fluoropolymer than is substantiallyfree of interpolymerized units of vinylidene fluoride or microstructuresequences of a carbon bonded hydrogen atom between carbon bondedfluorine atoms; and (b) a substantially non-fluorinated polymercomponent adhered to the first surface of the blend component, thenon-fluorinated polymer component (i) having one or more pendant primaryor secondary amine groups; and (ii) providing an exposed surface.
 2. Thecomposite article of claim 1 wherein the vinylidene-fluoride containingfluoropolymer of component (a) comprises interpolymerized units ofvinylidene fluoride or interpolymerized units of other monomers which,when polymerized, form a polymer microstructure sequence of a carbonbonded hydrogen atom between carbon bonded fluorine atoms.
 3. Thecomposite article of claim 1 wherein the vinylidene-fluoride containingfluoropolymer of component (a) comprises a fluoropolymer ofinterpolymerized units derived from (i) at least one fluorine-containingmonomer selected from the group of vinylidene fluoride,trifluoroethylene, 1-hydropentafluoropropylene,2-hydropentafluoropropylene, and, optionally, (ii) at least one monomercopolymerizable therewith.
 4. The composite article of claim 3 whereinthe monomer (ii) is selected from a fluorine-containing monomer, afluorine-free, unsaturated olefin monomer, an iodine- or abromine-containing unsaturated olefin monomer, or a combination thereof.5. The composite article of claim 4 wherein (a) the fluorine-containingmonomer is selected from the group consisting of hexafluoropropylene,tetrafluoroethylene, chlorotrifluoroethylene, a fluorinated vinyl ether,and a fluoride-containing di-olefin; (b) the fluorine-free, unsaturatedolefin monomer is selected from ethylene, propylene, or butadiene; and(c) the iodide- or bromide-containing unsaturated olefin monomer isselected from the group consisting of bromodifluoroethylene,bromotrifluoroethylene, iodotrifluoroethylene, and 4-bromo-3,3,4,4-tetrafluoro-1-butene.
 6. The composite article of claim 5 wherein thefluorine containing monomer is hexafluoropropylene.
 7. The compositearticle of claim 1 wherein the substantially non-vinylidenefluoride-containing fluoropolymer of component (a) is formed ofinterpolymerized units of (i) fluorine-containing monomers selected fromthe group consisting of hexafluoropropylene, tetrafluoroethylene,chlorotrifluoroethylene, a fluorinated vinyl ether, and combinationsthereof, and optionally, (ii) a fluorine-free unsaturated olefincomonomers, and optionally, (iii) an iodine- or bromine-containingunsaturated olefin monomer.
 8. The composite article of claim 7 whereinthe fluorine-free unsaturated olefin monomer is selected from ethylene,propylene, or butadiene, and the iodine- or bromine-containingunsaturated olefin monomer is selected from bromodifluoroethylene,bromotrifluoroethylene, iodotrifluoroethylene, or4-bromo-3,3,4,4-tetrafluoro-1-butene.
 9. The composite article of claim7 wherein the substantially non-vinylidene fluoride-containingfluoropolymer of component (a) is formed of interpolymerized units oftetrafluoroethylene and at least one other monomer selected from thegroup consisting of hexafluoropropylene, a fluorinated vinyl ether,ethylene, and propylene.
 10. The composite article of claim 1 whereinthe component (b) is selected from a polyamide, a polyimide, apolyurethane, a polyolefin, a polystyrene, a polyester, a polycarbonate,a polyketone, a polyurea, a polyarcylate, or a polymethacrylate.
 11. Thecomposite article of claim 1 wherein the component (b) is an elastomer.12. The composite article of claim 1 wherein the pendant amine group isa primary amine group.
 13. The composite article of claim 1 wherein theblend component comprises about 5% by weight to about 75% by weight ofthe vinylidene fluoride containing fluoropolymer, and about 25% byweight to about 95% by weight of the substantially non-vinylidenefluoride containing fluoropolymer.
 14. The composite article of claim 1wherein the blend component comprises about 10% by weight to about 75%by weight of the vinylidene fluoride containing fluoropolymer, and about25% by weight to about 90% by weight of the substantially non-vinylidenefluoride containing fluoropolymer.
 15. The composite article of claim 1wherein the blend component comprises about 10% by weight to about 50%by weight of the vinylidene fluoride containing fluoropolymer, and about50% by weight to about 90% by weight of the substantially non-vinylidenefluoride containing fluoropolymer.
 16. The composite article of claim 1which is shaped.
 17. The composite article of claim 16 selected from thegroup of a wire coating, a tube, a container, a sheet, a cable jacket,and a film.
 18. The composite article of claim 1 further comprising (c)a second substantially non-fluorinated polymer component adhered to theexposed surface of the component (b).
 19. The composite article of claim18 wherein the component (c) is selected from a polyamine, a polyimide,a polyurethane, a polyolefin, a polystyrene, a polyester, apolycarbonate, a polyketone, a polyurea, a polyacrylate, or apolymethacrylate.
 20. The composite article of claim 18 wherein thecomponent (c) is an elastomer.
 21. The composite article of claim 18wherein the component (c) is a polyamide.
 22. The composite article ofclaim 18 further comprising (d) a fourth component comprising a secondsubstantially non-vinylidene fluoride containing fluoropolymer that issubstantially free of interpolymerized units of vinylidene fluoride ormicrostructure sequences of a carbon bonded hydrogen atom between carbonbonded fluorine atoms adhered to the second surface of the blendcomponent (a). wherein a peel strength value between the blend component(a) and the component (b) is greater than a peel strength value betweenthe component (d) and the component (b).
 23. The composite article ofclaim 22 wherein the second substantially non-vinylidenefluoride-containing fluoropolymer of component (d) is formed ofinterpolymerized units of (i) fluorine-containing monomers selected fromthe group consisting of hexafluoropropylene, tetrafluoroethylene,chlorotrifluoroethylene, a fluorinated vinyl ether, and combinationsthereof, and optionally, (ii) a fluorine-free unsaturated olefincomonomer, and optionally, (iii) an iodine- or bromide-containingunsaturated olefin monomer.
 24. The composite article of claim 23wherein the fluorine-free unsaturated olefin monomer is selected fromethylene, propylene, or butadiene, and the iodide- or bromide-containingolefin monomer is selected from bromodifluoroethylene,bromotrifluoroethylene, iodotrifluoroethyene,4-bromo-3,3,4,4-tetrafluoro-1-butene.
 25. The composite article of claim23 wherein the second substantially non-vinylidene fluoride-containingfluoropolymer of component (d) is formed of interpolymerized units oftetrafluoroethylene and at least one other monomer selected from thegroup consisting of hexafluoropropylene, a fluorinated vinyl ether,ethylene, and propylene.
 26. The composite article of claim 22 furthercomprising: (c) a second substantially non-fluorinated polymer componentadhered to the exposed surface of the component (b).
 27. The compositearticle of claim 26 further comprising additives in at least one of thecomponents.
 28. The composite article of claim 22 further comprisingadditives in at least one of the components.
 29. The composite articleof claim 18 further comprising additives in at least one of thecomponents.
 30. A composite article comprising: (a) a blend componenthaving first and second surfaces, the blend component comprising: (i) avinylidene fluoride containing fluoropolymer; and (ii) a substantiallynon-vinylidene fluoride containing fluoropolymer that is substantiallyfree of interpolymerized units of vinylidene fluoride or microstructuresequences of a carbon bonded hydrogen atom between carbon bondedfluorine atoms; and (b) a substantially non-fluorinated polymercomponent adhered to the first surface of the blend component, thenon-fluorinated polymer component (i) having one or more pendant primaryor secondary amine groups; and (ii) providing an exposed surface, and(c) a catalyst.
 31. The composite article of claim 30 wherein thecatalyst comprises a combination of an oregano-onium compound and anacid acceptor.
 32. The composite article of claim 30 wherein thecatalyst comprises an amine compound selected from an aliphatic, aryl,or amidine amine compound.
 33. The composite article of claim 30 whereinthe catalyst is selected from the group consisting of (i) anoregano-onium compound and an acid acceptor, and (ii) an amine compound.34. The composite article of claim 33 wherein the catalyst is theoregano-onium compound and the acid acceptor.
 35. The composite articleof claim 33 wherein the catalyst is the amine compound.
 36. Thecomposite article of claim 35 wherein the amine compound is selectedfrom an aliphatic, aryl, or amidine amine.
 37. The composite article ofclaim 30 wherein the catalyst is present in component (a).
 38. Thecomposite article of claim 30 wherein the catalyst is present incomponent (b).
 39. A multi-layer polymer article comprising, in order: afirst layer of a substantially non-vinylidene fluoride containingfluoropolymer that is substantially free of interpolymerized units ofvinylidene fluoride or microstructure sequences of a carbon bondedhydrogen atom between carbon bonded fluorine atoms; a second layercomprising blend of (i) a vinylidene fluoride containing fluoropolymer;and (ii) a substantially non-vinylidene fluoride containingfluoropolymer that is substantially free of interpolymerized units ofvinylidene fluoride or microstructure sequences of a carbon bondedhydrogen atom between carbon bonded fluorine atoms; a third layercomprising a substantially non-fluorinated polymer having one or morependant primary or secondary amine groups; and a fourth layer comprisinga substantially non-fluorinated polymer; wherein a peel strength betweenthe second layer and the third layer is greater than a peel strengthbetween the first layer and the third layer.
 40. The shaped compositearticle of claim
 39. 41. The shaped article of claim 40 selected from asheet, a hose, a tube, a wire coating, a cable jacket, and a container.42. A blend component having first and second surfaces, the blendcomponent comprising: (i) a vinylidene fluoride containing fluoroplasticcopolymer, wherein 22 % by weight to 36 % by weight of theinterpolymerized units are derived from at least one fluorine-containingmonomer selected from the group of vinylidene fluoride,trifluoroethylene, 1 -hydropentafluoropropylene, and 2-hydropentafluoropropylene, and wherein at least one comonomer in thecopolymer is HFP; and (ii) a substantially non-vinylidene fluoridecontaining fluoroplastic consisting of the polymerization product of oneor more fluorine containing monomers selected from HFP, TFE, afluorinated vinyl ether, and cure site monomers.
 43. The blend componentof claim 42 wherein the substantially non-vinylidene fluoride containingfluoroplastic consists essentially of interpolymerized units of TFE. 44.The blend component of claim 42 wherein the substantially non-vinylidenefluoride containing fluoroplastic consists of interpolymerized unitsderived from two or more fluorine containing monomers selected from HFP,TFE, a fluorinated vinyl ether, and cure site monomers.
 45. The blendcomponent of claim 42 further comprising an additive selected from thegroup of a polymer, a pigment, a tackifier, a filler, electricallyconductive materials, electrically insulative materials, a stabilizer,an antioxidant, a lubricant, a processing aid, an impact modifier, aviscosity modifier, and mixtures thereof.
 46. The blend component ofclaim 42 wherein the vinylidene fluoride containing fluoroplasticcomprises about 10% by weight to about 50 % by weight of the blend; andthe substantially non-vinylidene fluoride containing fluoroplasticcomprises about 50 % by weight to about 90 % by weight of the blend. 47.The blend component of claim 42 which is shaped, the shape optionallyselected from a wire coating, a tube, a container, a sheet, a cablejacket, and a film.
 48. The blend component of claim 42, wherein about22% by weight to about 36 % by weight of the interpolymerized units ofthe vinylidene fluoride containing fluoroplastic copolymer are derivedvinylidene fluoride.
 49. The blend component of claim 42, wherein thevinylidene fluoride containing fluoroplastic copolymer comprisesinterpolymerized units derived from VDF, HFP and TFE.
 50. The blendcomponent of claim 42, wherein the substantially non-vinylidene fluoridecontaining fluoropolymer consists of the polymerization product of HFPand TFE.
 51. A blend component having first and second surfaces, theblend component comprising: (i) a vinylidene fluoride containingfluoroplastic copolymer, wherein 3 % by weight to 36 % by weight of theinterpolymerized units are derived from fluorine-containing monomersselected from the group of vinylidene fluoride, trifluoroethylene, 1-hydropentafluoropropylene, and 2 -hydropentafluoropropylene; and (ii) asubstantially non-vinylidene fluoride containing fluoroplasticconsisting of interpolymerized units formed from polymerizing two ormore monomers selected from HFP, TFE, CTFE, a fluorinated vinyl ether,and cure site monomers.
 52. The blend component of claim 51 wherein thevinylidene-fluoride containing fluoroplastic comprises a fluoropolymerof interpolymerized units derived from (A) at least onefluorine-containing monomer selected from the group of vinylidenefluoride, trifluoroethylene, 1 -hydropentafluoropropylene, and 2-hydropentafluoropropylene; and, (B) at least one monomercopolymerizable therewith, wherein the monomer (B) is selected from afluorine-containing monomer, a fluorine-free, unsaturated olefinmonomer, an iodine- or a bromine-containing unsaturated olefin monomer,or a combination thereof.
 53. The blend component of claim 52 wherein(a) the fluorine-containing monomer is selected fromhexafluoropropylene, tetrafluoroethylene, chlorotrifluoroethylene, afluorinated vinyl ether, and a fluorine-containing di-olefin; (b) thefluorine-free, unsaturated olefin monomer is selected from ethylene,propylene, and butadiene; and (c) the iodide- or bromide-containingunsaturated olefin monomer is selected from bromodifluoroethylene,bromotrifluoroethylene, iodotrifluoroethylene, and 4 -bromo- 3,3,4,4-tetrafluoro- 1 -butene.
 54. The blend component of claim 51 wherein thefluoroplastic (ii) consists of interpolymerized units of (a) two or morefluorine-containing monomers selected from HFP, TFE, CTFE, a fluorinatedvinyl ether, and combinations thereof, and (b) at least one cure sitemonomer selected from an iodine- or bromine-containing unsaturatedolefin monomer.
 55. The blend component of claim 54 wherein the iodine-or bromine-containing unsaturated olefin monomer is selected frombromodifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene,and 4 -bromo- 3,3,4,4 -tetrafluoro- 1 -butene.
 56. The blend componentof claim 51 further comprising an additive selected from the group of apolymer, a pigment, a tackifier, a filler, electrically conductivematerials, electrically insulative materials, a stabilizer, anantioxidant, a lubricant, a processing aid, an impact modifier, aviscosity modifier, and mixtures thereof.
 57. The blend component ofclaim 51 wherein the vinylidene fluoride containing fluoroplasticcomprises about 10% by weight to about 50 % by weight of the blend; andthe substantially non-vinylidene fluoride containing fluoroplasticcomprises about 50 % by weight to about 90 % by weight of the blend. 58.The blend component of claim 51 which is shaped, the shape optionallyselected from a wire coating, a tube, a container, a sheet, a cablejacket, and a film.
 59. The blend component of claim 51, wherein atleast one monomer in the substantially non-vinylidene fluoridecontaining fluoroplastic is a fluorinated vinyl ether.
 60. The blendcomponent of claim 51, wherein about 22% by weight to about 36 % byweight of the interpolymerized units of the vinylidene fluoridecontaining fluoroplastic copolymer are derived from at least onefluorine-containing monomer selected from the group of vinylidenefluoride, trifluoroethylene, 1 -hydropentafluoropropylene, and 2-hydropentafluoropropylene.
 61. The blend component of claim 51, whereinabout 22% weight to about 36 % by weight of the interpolymerized unitsare derived from vinylidene fluoride.
 62. A composite articlecomprising: (a) a blend component having first and second surfaces, theblend component consisting of: (i) a vinylidene fluoride containingfluoroplastic copolymer, wherein 22 % by weight to 36 % by weight of theinterpolymerized units are derived from fluorine-containing monomersselected from the group of vinylidene fluoride, trifluoroethylene, 1-hydropentafluoropropylene, and 2 -hydropentafluoropropylene, andwherein at least one comonomer in the copolymer is HFP; and (ii) asubstantially non-vinylidene fluoride containing fluoroplastic that issubstantially free of interpolymerized units of vinylidene fluoride ormicrostructure sequences of a carbon bonded hydrogen atom bonded betweencarbon bonded fluorine atoms; and (b) a substantially non-vinylidenefluoride containing fluoroplastic component that is substantially freeof interpolymerized units of vinylidene fluoride or microstructuresequences of a carbon bonded hydrogen atom bonded between carbon bondedfluorine atoms adhered to a surface of the blend component (a).
 63. Thearticle of claim 62 wherein the substantially non-vinylidene fluoridecontaining fluoroplastic in the blend component and the substantiallynon-vinylidene fluoride containing fluoroplastic component are the samepolymer.
 64. The article of claim 62 wherein the substantiallynon-vinylidene fluoride containing fluoroplastic in the blend componentand the substantially non-vinylidene fluoride containing fluoroplasticcomponent are different fluoropolymers.
 65. The article of claim 62wherein the substantially non-vinylidene fluoride containingfluoroplastic in component (a) and/or (b) is a perfluoropolymer.
 66. Thearticle of claim 65 wherein the substantially non-vinylidene fluoridecontaining perfluoroplastic in component (a) and/or (b) comprisesinterpolymerized units of TFE.
 67. The article of claim 65 wherein thesubstantially non-vinylidene fluoride containing perfluoroplastic incomponent (a) and/or (b) consists essentially of interpolymerized unitsof TFE.
 68. The article of claim 62 wherein the vinylidene-fluoridecontaining fluoroplastic of component (a) comprises a fluoropolymer ofinterpolymerized units derived from (i) at least one fluorine-containingmonomer selected from the group of vinylidene fluoride,trifluoroethylene, 1 -hydropentafluoropropylene, 2-hydropentafluoropropylene, (ii) HFP, and (iii) at least one additionalmonomer copolymerizable therewith.
 69. The article of claim 68 whereinthe monomer (iii) is selected from a fluoride-containing monomer, afluorine-free, unsaturated olefin monomer, an iodine- or abromine-containing unsaturated olefin monomer, or a combination thereof.70. The article of claim 69 wherein (a) the fluorine-containing monomeris selected from tetrafluoroethylene, chlorotrifluoroethylene, afluorinated vinyl ether, and a fluorine-containing di-olefin; (b) thefluorine-free, unsaturated olefin monomer is selected from ethylene,propylene, and butadiene; and (c) the iodide- or bromide-containingunsaturated olefin monomer is selected from bromodifluoroethylene,bromotrifluoroethylene, iodotrifluoroethylene, and 4 -bromo- 3,3,4,4-tetrafluoro- 1 -butene.
 71. The article of claim 62 wherein thesubstantially non-vinylidene fluoride-containing fluoropolymer ofcomponent (a) is formed of interpolymerized units of (i)fluorine-containing monomers selected from hexafluoropropylene,tetrafluoroethylene, chlorotrifluoroethylene, a fluorinated vinyl ether,and combinations thereof, and optionally, (ii) a fluorine-freeunsaturated olefin comonomer, and optionally, (iii) an iodine- orbromine-containing unsaturated olefin monomer.
 72. The article of claim71 wherein the fluorine-free unsaturated olefin monomer is selected fromethylene, propylene, and butadiene, and the iodine- orbromine-containing unsaturated olefin monomer is selected frombromodifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene,and 4 -bromo- 3,3,4,4 -tetrafluoro- 1 -butene.
 73. The article of claim71 wherein the substantially non-vinylidene fluoride-containingfluoroplastic of component (a) is formed of interpolymerized units oftetrafluoroethylene and at least one other monomer selected fromhexafluoropropylene, a fluorinated vinyl ether, ethylene, and propylene.74. The article of claim 62 wherein component (b) further comprises anadditive selected from a polymer, a pigment, a tackifier, a filler,electrically conductive materials, electrically insulative materials, astabilizer, an antioxidant, a lubricant, a processing aid, an impactmodifier, a viscosity modifier, and mixtures thereof.
 75. The article ofclaim 62 wherein the blend component comprises about 5% by weight toabout 75 % by weight of the vinylidene fluoride containingfluoroplastic; and about 25 % by weight to about 95 % by weight of thesubstantially non-vinylidene fluoride containing fluoroplastic.
 76. Thearticle of claim 62 which is shaped, the shape optionally selected froma wire coating, a tube, a container, a sheet, a cable jacket, and afilm.
 77. The composite article of claim 62, wherein the substantiallynon-vinylidene fluoride containing fluoroplastic in the blend componentconsists essentially of the polymerization product of one or morefluorine containing monomers selected from HFP, TFE, a fluorinated vinylether, and cure site monomers.
 78. A blend component having first andsecond surfaces, the blend component comprising: (i) a vinylidenefluoride containing fluoroplastic copolymer consisting ofinterpolymerized units formed from (a) a fluorine-containing monomerselected from the group consisting of vinylidene fluoride,trifluoroethylene, 1 -hydropentafluoropropylene, 2-hydrofluoropentafluoropropylene, and combinations thereof; and (b) atleast one monomer copolymerizable therewith selected from the groupconsisting of HFP, TFE, a cure site monomer, and combinations thereof:wherein 3 % by weight to 36 % by weight of the interpolymerized unitsare derived from (a); and (ii) a substantially non-vinylidene fluoridecontaining fluoroplastic consisting of the polymerization product of oneor more fluorine containing monomers selected from HFP, TFE, CTFE, andcure site monomers.
 79. The blend component of claim 78 furthercomprising an additive selected from the group of a polymer, a pigment,a tackifier, a filler, electrically conductive materials, electricallyinsulative materials, a stabilizer, an antioxidant, a lubricant, aprocessing aid, an impact modifier, a viscosity modifier, and mixturesthereof.
 80. The blend component of claim 78 wherein the vinylidenefluoride containing fluoroplastic comprises about 10% by weight to about50 % by weight of the blend; and the substantially non-vinylidenefluoride containing fluoroplastic comprises about 50 % by weight toabout 90 % by weight of the blend.
 81. The blend component of claim 78which is shaped, the shape optionally selected from a wire coating, atube, a container, a sheet, a cable jacket, and a film.